CN110055066A - A kind of red fluorescence powder and preparation method thereof - Google Patents
A kind of red fluorescence powder and preparation method thereof Download PDFInfo
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- CN110055066A CN110055066A CN201910216616.5A CN201910216616A CN110055066A CN 110055066 A CN110055066 A CN 110055066A CN 201910216616 A CN201910216616 A CN 201910216616A CN 110055066 A CN110055066 A CN 110055066A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The invention discloses a kind of red fluorescence powder, chemical general formulas are as follows: Ca2‑xAEuxBx(MoyW1‑y)O6, wherein A=Ca, Mg, Zn, Ba, Sr；B=Li, Na, K；0<x<1；0<y<1.The present invention also provides a kind of preparation methods of red fluorescence powder, calcium carbonate, the oxide of A, europium oxide, the carbonate of B, tungsten oxide, molybdenum oxide are weighed by said ratio, above-mentioned substance is ground and mixed, then after the raw material of mixing being calcined a period of time at a certain temperature, it is cooled to room temperature, up to product after ball milling.Red fluorescence powder chemical stability of the invention is good, and launching efficiency is high, can be in the emitting red light of near ultraviolet (395nm), blue light (467nm) excitation acquisition 616nm or so.It can be matched near ultraviolet and blue-ray LED, be a kind of novel red fluorescent powder for white radiation LED.
Description
Technical field
The present invention relates to fluorescent material preparation technical fields more particularly to a kind of red fluorescence powder and preparation method thereof.
Background technique
White light emitting diode (LED) has high photosynthetic efficiency, low energy consumption, long-life, nothing as new generation of green illuminating product
The advantages that pollution, is successfully applied in semiconductor lighting and LCD backlight display field.Currently, the realization of white light LEDs
Technology is broadly divided into three kinds: first is that multi-chip method, with the LED chip of three kinds of colors of red, green, blue, and using three primary color theory, according to
Certain proportion combination issues white light, and this method is since the bias of different chips is different, and circuit control is more demanding, and cost is very
It is high.Second is that fluorescent powder transformation approach, this method is the technology of current application acquisition white light LEDs the most mature, and this method obtains
Cost is relatively low for white light, but since this fluorescent powder lacks red color light component, so colour rendering index is bad, colour temperature is higher, is not easy to adjust
Section.Third is that integrated chip method, is so that LED chip is directly issued white light using multiple active layers in a chip.This method
Since red fluorescence powder is low relative to Blue-green phosphor luminous efficiency, obtained white light energy conversion ratio is low, and stability is poor.Thus
As it can be seen that fluorescent powder plays the role of vital as the transformational substance of light, the luminescent properties of fluorescent powder directly influence white
The luminous efficiency of light LED product, the main indicators such as service life, colour rendering index, colour temperature.
The red fluorescence powder being commercialized now is mainly sulfide and nitride.Wherein the most widely used is Y2O2S:
Eu3+, however the physical instability of this fluorescent powder, sulfide gas is discharged under ultraviolet light, service life is short, dirty
Environment is contaminated, luminous efficiency is poor, although nitride customer service disadvantage mentioned above, expensive.Therefore new and effective red fluorescence
The Development Techniques of powder are of great significance for the development of white light LEDs.
Summary of the invention
The purpose of the present invention is to provide a kind of red fluorescence powders and preparation method thereof, solve and emit light in the prior art
The red color light component of spectrum is few and the problem of keeping its colour rendering index relatively low, single white light cannot be synthesized, and red fluorescence of the invention
Powder chemical stability is good, and launching efficiency is high, can be excited simultaneously by near ultraviolet and blue light.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of red fluorescence powder, chemical general formula
Are as follows: Ca2-xAEuxBx(MoyW1-y)O6, wherein A=Ca, Mg, Zn, Ba, Sr；B=Li, Na, K；0<x<1；0<y<1.
Preferably, work as A=Zn, when B=Na, light-emitting phosphor performance of the invention is best.
The present invention also provides a kind of preparation methods of red fluorescence powder, and the oxidation of calcium carbonate, A are weighed by said ratio
Object, europium oxide, the carbonate of B, tungsten oxide, molybdenum oxide, above-mentioned substance is ground and is mixed, then by the raw material of mixing certain
Temperature lower calcination for a period of time after, be cooled to room temperature, up to product after ball milling.
Further, to keep raw material grinding more abundant and being easy to mix, ethyl alcohol is added during grinding and mixing.
Preferably, calcination temperature is 1300 DEG C.
Preferably, calcination time 6-12h.
Since certain damage can be caused to the surface topography of fluorescent powder in high-temperature burning process, in order to improve solid phase
The great efforts of method synthetic product particle, the problems such as being unevenly distributed, the present invention is in advance handled the presoma of raw material, then is added
Add fluxing agent etc. to be improved, studies have shown that be used in preparatory ball milling, then carries out being heat-treated prepared sample particle more equal
One.
The present invention uses the optical property of trans cis photoisomerization instrument test sample, shows that red of the invention is glimmering by test
Light powder chemical stability is good, and launching efficiency is high, can obtain 616nm's or so near ultraviolet (395nm), blue light (467nm) excitation
Emitting red light.It can be matched near ultraviolet and blue-ray LED, be a kind of novel red fluorescent powder for white radiation LED.
Detailed description of the invention
Fig. 1 is the light-emitting phosphor map of the embodiment of the present invention 1；
Fig. 2 is the light-emitting phosphor map of the embodiment of the present invention 2；
Fig. 3 is the light-emitting phosphor map of the embodiment of the present invention 5；
Fig. 4 is the luminous map of sample of 6Mo of embodiment of the present invention doping；
Fig. 5 is 6 fluorescent powder Ca of the embodiment of the present invention1.6ZnEu0.4MoxW1-xO6Luminous intensity and x value relation curve.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, but do not constitute limiting the scope of the invention.
Embodiment 1
Prepare red fluorescence powder Ca1.5ZnEu0.5WO6
CaCO is weighed by stoicheiometry31.5014 grams of (analysis is pure), WO32.3185 grams of (analysis is pure), Eu2O3(99.99%)
0.8798 gram, 0.8139 gram of ZnO (analysis is pure).15ml dehydrated alcohol is added, is fully ground with agate mortar, is uniformly mixed postposition
In corundum crucible, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.According to above-mentioned side
Method, can synthesize chemical general formula is Ca1.5AEu0.5WO6The red fluorescence powder of (A=Ca, Mg, Zn, Ba, Sr).As shown in Figure 1,
Under 466nm excitation wavelength, the luminous intensity variations of fluorescent powder are as follows: ZnCa1.5Eu0.5WO6>MgCa1.5Eu0.5 WO6>
SrCa1.5Eu0.5WO6>BaCa1.5Eu0.5WO6>Ca2.5Eu0.5WO6, the doping of metal ion causes Ca2.5Eu0.5WO6Fluorescent powder
Centre of luminescence local microstructure change in original crystal field structure, to affect the luminous intensity of fluorescent powder.
Embodiment 2
Prepare red fluorescence powder Ca1.6ZnEu0.4WO6
CaCO is weighed by stoicheiometry31.5014 grams of (analysis is pure), WO32.3185 grams of (analysis is pure), Eu2O3(99.99%)
0.8798 gram, 0.8139 gram of ZnO (analysis is pure).15ml dehydrated alcohol is added, is fully ground with agate mortar, is uniformly mixed postposition
In corundum crucible, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.By taking 0.1≤x
≤ 0.7, Ca can be prepared1.5ZnEuxWO6(x=0.1-0.7) relation curve of red light emitting phosphor intensity and x value, by
Shown in Fig. 2, increase, the luminous intensity as x=0.5 in the luminous intensity of 466nm emission spectrum, product with the increase of x value
Reach maximum, continues to increase with x value, the luminous intensity of fluorescent powder is begun to decline, and the optimal value of x is between 0.4-0.6.
Embodiment 3
Prepare red fluorescence powder Ca1.2ZnEu0.4Na0.4WO6
Weigh CaCO31.2012 grams of (analysis is pure), WO32.3186 grams of (analysis is pure), Eu2O3(99.99%) 0.7033 gram,
Na2CO315ml dehydrated alcohol is added in (analysis is pure) 0.2120 gram of, is fully ground with agate mortar, is put into corundum after mixing
In crucible, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.The transmitting light of gained fluorescent powder
Spectrum such as Fig. 3 (excitation wavelength 466nm).
Embodiment 4
Prepare red fluorescence powder Ca1.2ZnEu0.4Li0.4WO6
Weigh CaCO31.2013 grams of (analysis is pure), WO32.3186 grams of (analysis is pure), Eu2O3(99.99%) 0.7039 gram,
Li2CO315ml dehydrated alcohol is added in (analysis is pure) 0.1478 gram of, is fully ground with agate mortar, is put into corundum after mixing
In crucible, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.The transmitting light of gained fluorescent powder
Spectrum such as Fig. 3 (excitation wavelength 466nm).
Embodiment 5
Prepare red fluorescence powder Ca1.2ZnEu0.4K0.4WO6
Weigh CaCO31.2019 grams of (analysis is pure), WO32.3186 grams of (analysis is pure), Eu2O3(99.99%) 0.7038 gram,
K2CO315ml dehydrated alcohol is added in (analysis is pure) 0.2765 gram of, is fully ground with agate mortar, is put into corundum earthenware after mixing
In crucible, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.The emission spectrum of gained fluorescent powder
Such as Fig. 3 (excitation wavelength 466nm).
As shown in Figure 3, Na+As charge compensator relative to Li+、K+Effect to get well, Li+、Na+As charge compensator
Incorporation, the luminous intensity of the red fluorescence powder can be made to enhance, K+Fluorescence is reduced instead as charge compensator incorporation
The luminous intensity of powder.The shape of its excitation and emission spectra does not change.
Embodiment 6
Prepare red fluorescence powder CaZnEu0.4Mo0.2W0.8O6
Weigh CaCO31.6014 grams of (analysis is pure), WO31.8548 grams of (analysis is pure), Eu2O3(99.99%) 0.7038 gram,
0.8139 gram of ZnO (analysis is pure), MoO315ml dehydrated alcohol is added in (analysis is pure) 0.2879 gram of, is fully ground with agate mortar,
It is put into corundum crucible after mixing, feeding Muffle furnace is after 1300 DEG C of calcining 6h, cooling with ball mill grinding up to product.
As seen from Figure 4, compared with the sample for not carrying out Mo doping, band-like excitation spectrum becomes wider, near ultraviolet long wavelength
Direction is expanded, and gets higher its launching efficiency, and maintain original excitation intensity at 395nm and 466nm, with LED chip
It is wider to match excitation wavelength range, is suitble near ultraviolet and blue-ray LED excitation.According to the method described above, it synthesizes
Ca1.6ZnEu0.4MoxW1-xO6Red fluorescence powder series, the value range of x are 0≤x≤1, fluorescent powder Ca1.6ZnEu0.4MoxW1-xO6
Luminous intensity and x value relation curve such as Fig. 5 (excitation wavelength 466nm).As seen from Figure 5, Mo, W are co-doped with so that glimmering
The luminous intensity of light powder increases, as x=0.2, red fluorescence powder Ca1.6ZnEu0.4Mo0.2W0.8O6Luminous intensity reach most
Greatly.
The present invention goes out CaZnEu using ball milling Solid phase synthesis0.4Mo0.2W0.8O6Red fluorescence powder, using photoluminescence light
Spectrometer tests its optical property, and the red fluorescence powder is suitable near ultraviolet and blue chip as the result is shown, has at 616nm strong
Red emission.Show that red fluorescence powder chemical stability of the invention is good by test, launching efficiency is high, can be near ultraviolet
The excitation of (395nm), blue light (467nm) obtains the emitting red light of 616nm or so.It can be matched near ultraviolet and blue-ray LED, be a kind of
Novel red fluorescent powder for white radiation LED.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (6)
1. a kind of red fluorescence powder, which is characterized in that its chemical general formula are as follows: Ca2-xAEuxBx(MoyW1-y)O6, wherein A=Ca,
Mg,Zn,Ba,Sr；B=Li, Na, K；0<x<1；0<y<1.
2. red fluorescence powder according to claim 1, it is characterised in that: A=Zn, B=Na.
3. a kind of preparation method of red fluorescence powder, it is characterised in that: weigh calcium carbonate, the oxide of A, oxidation by said ratio
Europium, the carbonate of B, tungsten oxide, molybdenum oxide, above-mentioned substance is ground and is mixed, then at a certain temperature by the raw material of mixing
It after calcining a period of time, is cooled to room temperature, up to product after ball milling.
4. a kind of preparation method of red fluorescence powder according to claim 3, it is characterised in that: in the mistake ground and mixed
Ethyl alcohol is added in journey.
5. a kind of preparation method of red fluorescence powder according to claim 3, it is characterised in that: calcination temperature 1300
℃。
6. a kind of preparation method of red fluorescence powder according to claim 3, it is characterised in that: calcination time 6-12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607396A (en) * | 2020-06-10 | 2020-09-01 | 蕉岭佰霖生物科技有限公司 | Near ultraviolet broadband excited red fluorescent powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786929A (en) * | 2012-07-31 | 2012-11-21 | 南京大学 | Red phosphor |
| CN106190119A (en) * | 2016-07-20 | 2016-12-07 | 上海应用技术学院 | A kind of white light LEDs Eu3+the preparation method of doping molybdenum hydrochlorate Hydrargyri Oxydum Rubrum |
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- 2019-03-21 CN CN201910216616.5A patent/CN110055066A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786929A (en) * | 2012-07-31 | 2012-11-21 | 南京大学 | Red phosphor |
| CN106190119A (en) * | 2016-07-20 | 2016-12-07 | 上海应用技术学院 | A kind of white light LEDs Eu3+the preparation method of doping molybdenum hydrochlorate Hydrargyri Oxydum Rubrum |
Non-Patent Citations (2)
| Title |
|---|
| K.V. DABRE ET AL.: "Synthesis and photoluminescence properties of Eu3+, Sm3+ and Pr3+ doped Ca2ZnWO6 phosphors for phosphor converted LED", 《JOURNAL OF LUMINESCENCE》 * |
| LI LI ET AL.: "Luminescence enhancement in the Sr2ZnW1-xMoxO6:Eu3+,Li+ phosphor for near ultraviolet based solid state lighting", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607396A (en) * | 2020-06-10 | 2020-09-01 | 蕉岭佰霖生物科技有限公司 | Near ultraviolet broadband excited red fluorescent powder and preparation method thereof |
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